US4084954A - Biocidally-active 1,3-benzodithiole-2-one compounds - Google Patents

Biocidally-active 1,3-benzodithiole-2-one compounds Download PDF

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Publication number
US4084954A
US4084954A US05/618,255 US61825575A US4084954A US 4084954 A US4084954 A US 4084954A US 61825575 A US61825575 A US 61825575A US 4084954 A US4084954 A US 4084954A
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US
United States
Prior art keywords
compound
benzodithiole
nitro
trifluoromethyl
growing plants
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US05/618,255
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English (en)
Inventor
Khalid Rasheed
James D. Warkentin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ansul Co
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Ansul Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ansul Co filed Critical Ansul Co
Priority to US05/618,255 priority Critical patent/US4084954A/en
Priority to SE7610167A priority patent/SE7610167L/xx
Priority to CA262,195A priority patent/CA1071200A/en
Priority to JP51118400A priority patent/JPS5265270A/ja
Priority to FR7629310A priority patent/FR2326424A1/fr
Priority to BR7606511A priority patent/BR7606511A/pt
Priority to CH1230576A priority patent/CH620338A5/fr
Priority to AR264928A priority patent/AR221323A1/es
Priority to AU18287/76A priority patent/AU503926B2/en
Priority to NL7610834A priority patent/NL7610834A/xx
Priority to GB6507/79A priority patent/GB1567482A/en
Priority to DE19762644036 priority patent/DE2644036A1/de
Priority to GB40675/76A priority patent/GB1567481A/en
Priority to BE171123A priority patent/BE846802A/xx
Priority to MX764947U priority patent/MX4134E/es
Priority to US05/821,977 priority patent/US4187096A/en
Priority to US05/821,978 priority patent/US4139362A/en
Priority to US05/848,721 priority patent/US4175186A/en
Priority to US05/860,455 priority patent/US4177270A/en
Application granted granted Critical
Publication of US4084954A publication Critical patent/US4084954A/en
Assigned to ANSUL COMPANY, THE reassignment ANSUL COMPANY, THE ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: CIBA-GEIGY CORPORATION
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D339/00—Heterocyclic compounds containing rings having two sulfur atoms as the only ring hetero atoms
    • C07D339/02—Five-membered rings
    • C07D339/06—Five-membered rings having the hetero atoms in positions 1 and 3, e.g. cyclic dithiocarbonates

Definitions

  • This invention relates generally to new and useful biocidally active compounds. More specifically, it relates to novel 1,3-benzodithiole-2-one and 1,3-benzodithiole-2-thione compounds prepared by an unusual but highly simple and convenient cyclization reaction. In fact, it is due to this synthesis that the numerous derivatives disclosed herein can be obtained so easily and in good yields.
  • novel compounds of this invention are useful in treating pests associated with with growing plants in order to beneficially enhance the growth and/or yield-potential of said growing plants. This is accomplished by applying a biocidally active amount of the subject compound to soil, seed or the growing plant.
  • pests as used herein is meant to include plant pests such as weeds and fungi, and animal pests such as arachnids, nematodes, or insects.
  • the concentration, rate and physical form of the administered compound are determined by the particular application, said application comprising one or more of the following:
  • treating pests associated with growing plants signifies the application of a compound as herein defined to pests associated with growing plants which embraces germinating plants, e.g. seeds, sprouts, seedlings, and fully grown plants.
  • the mode of application will depend on the desired end use. For example, if the treatment is for pre-emergent herbicidal use, the compound will be administered into the soil which contains the growing seeds. In contrast, when used as a post-emergent herbicide, the compound will be applied to the growing plants after seeds have germinated.
  • treatment comprises foliar fungicidal application
  • the compound is administered, as a spray, directly onto the leaves and other above ground portions of diseased plants.
  • the compound may be applied by contacting the leaves (or plant) directly or as a soil incorporation in the soil where the plant is growing.
  • the compound is usually applied as a seed treatment, or as a drench and/or incorporation to the soil containing the seed or the growing plant.
  • the compound is normally applied directly as a drench and/or incorporation to the soil containing the growing plant.
  • the compound is usually applied topically to the above ground portions of infested plants and/or to the soil containing the growing plants.
  • biocidally active amount means an amount of compound which effectively permits the desired objective.
  • this invention is concerned with compounds of the formula: ##STR1## wherein W is O or S; Y is selected from hydrogen, cyano, alkylsulfonyl, nitro and trifluoromethyl; X is selected from alkyl and alkenyl of up to 6 carbon atoms, nitro, trichloromethyl, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, trifluoromethylsulfoxyl, trifluoromethylsulfonyl, methoxymethyl, cyano, carboxy, carbamyl, halogen (F, Cl, Br, I), hydroxy, acetylamino, amino, N-phenylamino, N,N-diallylamino, alkoxy, N-morpholino, N-piperidino, N-piperazino, N-pyrrolidino, dimethylaminodithiocarbamyl, carboalkoxy, alkylthio, mono- and di- and di
  • novel compounds of this invention are prepared by a novel procedure wherein a unique cyclization step is involved. It is this synthetic method which allows for the formation of the numerous compounds disclosed herein. Compounds which would ordinarily be inaccessible or at best, tedious and difficult to make, are rendered available by an unusually simple and mild synthesis.
  • Y is selected from hydrogen, cyano, alkylsulfonyl, nitro and trifluoromethyl
  • X is selected from alkyl and alkenyl of up to 6 carbon atoms, nitro, trichloromethyl, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, trifluoromethylsulfoxyl, trifluoromethylsulfonyl, methoxymethyl, cyano, carboxy, carbamyl, halogen (F, Cl, Br, I), hydroxy, acetylamino, amino, N-phenylamino, N,N-diallylamino, alkoxy, N-morpholino, N-piperidino, N-piperazino, N-pyrrolidino, dimethylaminodithiocarbamyl, carboalkoxy, alkylthio, mono- and dialkylamino, N-alkyl
  • Starting material A is typically a halobenzene derivative, many of which are commercially available. If not, one can easily synthesize the desired compound using well-documented chemical techniques. As is apparent, the halo group (Z) and the adjacent nitro group both undergo substitution thereby effecting cyclization to form the heterocyclic 5-membered ring.
  • the other reagent, B is an N,N-dialkyldithiocarbamic acid or acid salt, such as the sodium salt.
  • the attractiveness of the above process is that under relatively mild conditions, using generally available or easily accessible reagents and in a single step, one can obtain the desired compounds in good yields.
  • the intermediate product C of this reaction can in many preparations be isolated. In others it undergoes the cyclization reaction, even at low temperatures, to produce final product D, the substituted 1,3-benzodithiole-2-ones.
  • the reaction process is carried out in the temperature range of from 0° to 200° C. In many instances, the reaction proceeds at room temperature or lower, whereas, in some cases, elevated temperatures may be desired in order to accelerate the reaction.
  • the reaction is usually carried out in a solvent, although the solvent may be omitted if effective dissolution of materials is possible.
  • a solvent is generally preferred, however, and it can be any solvent which does not enter into the reaction and in which the reactants are soluble to some extent. Suitable solvents are dimethylformamide, dimethylsulfoxide, acetone and methyl isobutyl ketone.
  • the mole ratio of reagents A and B is normally 1 to 1, however, it is generally preferred to use a slight excess of reagent B to ensure more complete reaction.
  • a co-product E is usually formed during the formation of desired product D.
  • This co-product is easily separated from product D using solvent differential properties. It is converted to compound D by treatment under basic conditions, such as sodium hydroxide in an aqueous solution or suspension containing solvent.
  • a typical solvent for such conversion is dimethylsulfoxide.
  • reaction is carried out at temperatures ranging from 0° to 200° C.
  • work-up is standard -- product is obtained by precipitation, washing, drying and recrystallization if necessary.
  • the 1,3-benzodithiole-2-thione compounds disclosed herein are obtained by conversion of the corresponding 1,3-benzodithiole-2-one compounds.
  • One way uses disodium trithiocarbonate as the sulfurizing agent.
  • Other suitable reagents include sodium hydrosulfide and potassium thiocyanate.
  • the biocidal processes of this invention comprise applying a biocidally effective amount of a compound disclosed herein to soil, seed or growing plant.
  • the compounds are formulated for use either as sprays made up by adding water to emulsifiable concentrates or wettable powders, as granules or as dispersions on carriers such as attapulgite clay granules, peat moss, fertilizer, vermiculite, etc.
  • the compounds are quite insoluble in water, and hence, for the preparation of emulsions or wettable powders, the compounds are preferably formulated with wetting agents.
  • the acid-addition and base-addition salts are within the purview of this invention.
  • the acid-addition salts are easily prepared by treating the amine base with a substantially equimolar amount of a chosen acid in an aqueous solution or in a suitable organic solvent such as methanol or ethanol.
  • a suitable organic solvent such as methanol or ethanol.
  • the only restriction on the acid used is that it provides acceptable ions, i.e., those which do not deleteriously affect the growing plants.
  • the base-addition salts are prepared in a similar manner except that base instead of acid is added. The same restriction with respect to acceptable ions applies.
  • the compounds disclosed herein are applied at a rate of from 0.5 lbs a.i./acre to 8.0 lbs a.i./acre.
  • the compounds disclosed herein are applied at a rate of from 0.25 to 40.0 lbs a.i./acre.
  • the compounds disclosed herein are applied at a rate of from 2.0 to 10.0 ounces per 100 lbs. of crop seed.
  • the compounds disclosed herein are applied at a rate of about 200 parts per million in a suitable solvent, such as water.
  • the compounds disclosed herein are applied at a rate of from 30 to 1000 parts per million in a suitable solvent, such as water.
  • the compounds disclosed herein are applied at a rate of from 15 to 20 parts per million in a suitable solvent, such as water.
  • the compounds disclosed herein are applied at a rate of from 0.2% to 10.0% in a suitable solvent, such as water.
  • reaction mixture was stirred at 5°-10° C. for 90 minutes and thereafter for 18 hours at room temperature.
  • Example I The procedure of Example I is repeated wherein the following chlorobenzene derivatives are used in place of 2-6-dinitro-4-trifluoromethylchlorobenzene to provide the corresponding products:
  • Example IV The compounds enumerated in Example IV are converted to the corresponding 1,3-benzodithiole-2-thiones in accordance with the procedure outlined in Example III.
  • Example I The procedure of Example I is repeated wherein the following N,N-dialkyldithiocarbamic acid compounds in stoichiometric equivalent amounts are used in place of N,N-dimethyldithiocarbamic acid sodium salt dihydrate with comparable results:
  • Example II The procedure of Example I is repeated wherein the following solvents are used in place of acetone with comparable results:
  • the compound of Example I is prepared in the following manner: To a magnetically stirred solution of 16.2 g (60 mmoles) 2,6-dinitro-4-trifluoromethylchlorobenzene in 60 ml dimethylsulfoxide was added dropwise a solution of 10.74 g (60 mmoles) sodium dimethyldithiocarbamic acid. The reaction is mildly exothermic and accompanied by evolution of oxides of nitrogen. After allowing the reaction mixture to stir for 3 hours, 450 ml water and 225 ml chloroform are added and, after shaking well in an extraction funnel, the chloroform extract was withdrawn and the aqueous phase similarly extracted with two more 220 ml portions of chloroform.
  • Example VIII The procedure of Example VIII is repeated wherein the following halobenzene derivatives are used in place of 2.6-dinitro-4-trifluoromethylchlorobenzene to provide corresponding products:
  • the flats are planted with the desired plant species 7 - 9 days prior to spraying. By spraying time a well established flat of plants is ready for spraying.
  • the flats are prepared and planted with seed of the various species. A sheet of plastic is then placed over the seed and a measured quantity of screened soil normally used for covering the seed is placed on top. The flat is then ready for spraying. After spraying, the soil on top of the sheet of plastic is mixed thoroughly and spread evenly over the surface of the flat.
  • the plant species used in herbicide screening are corn (Zea mays L.), wheat (Triticum avesticum L.), cotton (Gossypium hirsutum L), soybeans (Glycine max L.), barnyardgrass (Echinochloa crusgalli L. Beauv), foxtail (Setaria viridis L. Beauv), morningglory (Ipomea purpurea L. Roth), and pigweed (Amaranthus retroflexus L.).
  • the following screen was used: Two potato-dextrose-agar plates of the desired fungal organism are blended in a Waring blender with 50 mls of sterile water. The resulting mixture is added to 3000 g of sterile soil in a plastic bag and thoroughly blended. Cucumber seeds are planted in 4 oz. cups containing a measured amount of the inoculated soil mixture. Finally, 10 mls of the candidate compound at 40 lb/A is atomized as a drench over the prepared soil. After 14 days evaluations are made based on the number of surviving seedlings in the treated cup compared to the untreated check.
  • the organisms used in the primary soil fungicide screen are Rhizoctonia solani and Pythium ultimum.
  • the candidate compound is applied at 200 ppm to Bonny Best variety of tomato plants which have 2-4 true leaves.
  • the treated plants are held at a relative humidity of 100% for 48 hours allowing ideal conditions for fungal invasion to occur.
  • a spore suspension of early blight fungus (Alternaria solani) is prepared and sprayed on the plant until it reaches the point of runoff.
  • acaricidal activity for the herein disclosed compounds, the following screening procedure was used: To evaluate a compound as a contact acaricide, the solution is sprayed at 15 psi onto the leaves of bean seedlings infested with mites as a 0.1% concentration. The sprayed plants are inoculated 24 hours later. In the case of systemic testing, the chemical is added to the nutrient solution in which the bean seedling is growing at a concentration of 20 ppm. After three days, mites are added to the leaves grown in the treated solution. In both cases, five days later counts are made and percent kill determined.
  • Two spotted spider mites (Tetranychus urticae) are used in these tests and pinto beans (Phaseolus vulgaris) in the cotylendonary stage is the host plant species used.
  • nematocidal activity For determination of nematocidal activity for the herein disclosed compounds, the following screening procedure was used: The roots of established tomato plants, grown in the presence of root knot (Meloidogyne incognita) nematodes and with adequately galled roots, are cut into small segments. The root segments are added to sterile soil and thoroughly mixed. The root knot infested soil is allowed to set for three days. During this period many larva will emerge from the decaying plant roots yielding a high potential of root knot inoculum soil. A quantity of the soil mixture is added to 8 oz. cups. Finally, 10 mls of the candidate nematocide at 20 ppm is added to the infested soil and thoroughly blended.
  • the treated soil is removed from the jar and placed in an 8 oz. cup.
  • the treated soil is allowed to aerate for 48 hours.
  • cucumber seeds are planted in the treated soil.
  • evaluations are made based on the galls occurring on the developing cucumber seedlings.
  • the candidate compound was evaluated as an insecticide on screwworms at rates of 0.3125-10.0%.
  • the solutions were applied on 1st, 2nd, and 3rd instar larvi and on eggs.
  • White fly infested tobacco (Nicotiana) plants were sprayed with a 1% solution of candidate test compound. Within 12 hours after application of the chemical, all white flies were either dead or had left the tabacco plants. White fly populations were too large to make quantitative counts, so visual observations were made.
  • the candidate compounds were applied in a 0.5% solution to pea aphids and pea seedling plants in a contact test using a Waters vertical spray tower.
  • the spray descends through an 8 inch stainless steel cylinder to the test insects and plants 44 inches below the atomizer.
  • the spray tower is operated at 10 p.s.i. and discharges about 30 milliliters of spray per minute through a Devilbiss atomizer.
  • the insects and seedlings were sprayed for a 15 second period and held for forty-eight hour mortality determinations.
  • Excised lima bean leaves were dipped into 0.05% solutions of the candidate compounds and when dry were offered to 10 larvae of the Southern armyworm (late third instar) for a 48 hour feeding period.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Heterocyclic Compounds Containing Sulfur Atoms (AREA)
US05/618,255 1975-09-30 1975-09-30 Biocidally-active 1,3-benzodithiole-2-one compounds Expired - Lifetime US4084954A (en)

Priority Applications (19)

Application Number Priority Date Filing Date Title
US05/618,255 US4084954A (en) 1975-09-30 1975-09-30 Biocidally-active 1,3-benzodithiole-2-one compounds
SE7610167A SE7610167L (sv) 1975-09-30 1976-09-14 Biocidalt aktiva foreningar
CA262,195A CA1071200A (en) 1975-09-30 1976-09-28 Biocidally-active 1, 3-benzodithiole-2-one and 1, 3-benzodithiole-2-thione compounds
FR7629310A FR2326424A1 (fr) 1975-09-30 1976-09-29 Procede de preparation de composes de la 1,3-benzodithiole-2-one et de la 1,3-benzodithiole-2-thione, ayant une activite biocide et leur procede de preparation
BR7606511A BR7606511A (pt) 1975-09-30 1976-09-29 Compostos biocidamente ativados processo para sua fabricacao e processo para tratar pragas
CH1230576A CH620338A5 (en)) 1975-09-30 1976-09-29
JP51118400A JPS5265270A (en) 1975-09-30 1976-09-29 1*33benzodithioll22one and 1*33benzothioll22 thione compound as agricultural chemicals
GB6507/79A GB1567482A (en) 1975-09-30 1976-09-30 Pesticidal use of benzodithioles
AU18287/76A AU503926B2 (en) 1975-09-30 1976-09-30 1, 3-BENZODITHIOLE-2-ONE (and 2-THIONIC) DERIVATIVES
NL7610834A NL7610834A (nl) 1975-09-30 1976-09-30 Werkwijze voor het bereiden van 1,3-benzodithio- feen-2-on en 1,3-benzodithiofeen-2-thionverbin- dingen met biocide activiteit.
AR264928A AR221323A1 (es) 1975-09-30 1976-09-30 Compuestos derivados de 1,3-benzoditiol-2-ona,utiles como herbicidas;composiciones que los contienen y procedimiento para prepararlos
DE19762644036 DE2644036A1 (de) 1975-09-30 1976-09-30 Biocid wirksame 1,3-benzodithiol-2- on und 1,3-benzodithiol-2-thion-verbindungen
GB40675/76A GB1567481A (en) 1975-09-30 1976-09-30 Benzodithiole derivatives
BE171123A BE846802A (fr) 1975-09-30 1976-09-30 Composes de 1,3-benzodithiole-2-one et de 1,3-benzodithiole-2-thione, et leur preparation
MX764947U MX4134E (es) 1975-09-30 1976-10-01 Procedimiento para la preparacion de los compuestos 1,3-benzoditiol-2-tiona
US05/821,977 US4187096A (en) 1975-09-30 1977-08-04 Biocidally-active 1,3-benzodithiole-2-thione compounds
US05/821,978 US4139362A (en) 1975-09-30 1977-08-04 Biocidally-active 1,2,3-benzotrisulfides
US05/848,721 US4175186A (en) 1975-09-30 1977-11-04 Biocidally-active, 1,3-benzodithiole-2-one and 1,3-benzodithiole-2-thione compounds
US05/860,455 US4177270A (en) 1975-09-30 1977-12-14 Soil fungicidal (nitrogen heterocyclic)-substituted-1,3-benzodithiole-2-ones

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US05/618,255 US4084954A (en) 1975-09-30 1975-09-30 Biocidally-active 1,3-benzodithiole-2-one compounds

Related Child Applications (4)

Application Number Title Priority Date Filing Date
US05/821,977 Continuation-In-Part US4187096A (en) 1975-09-30 1977-08-04 Biocidally-active 1,3-benzodithiole-2-thione compounds
US05/821,978 Continuation-In-Part US4139362A (en) 1975-09-30 1977-08-04 Biocidally-active 1,2,3-benzotrisulfides
US05/848,721 Division US4175186A (en) 1975-09-30 1977-11-04 Biocidally-active, 1,3-benzodithiole-2-one and 1,3-benzodithiole-2-thione compounds
US05/860,455 Division US4177270A (en) 1975-09-30 1977-12-14 Soil fungicidal (nitrogen heterocyclic)-substituted-1,3-benzodithiole-2-ones

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US4084954A true US4084954A (en) 1978-04-18

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US05/618,255 Expired - Lifetime US4084954A (en) 1975-09-30 1975-09-30 Biocidally-active 1,3-benzodithiole-2-one compounds
US05/821,978 Expired - Lifetime US4139362A (en) 1975-09-30 1977-08-04 Biocidally-active 1,2,3-benzotrisulfides

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US05/821,978 Expired - Lifetime US4139362A (en) 1975-09-30 1977-08-04 Biocidally-active 1,2,3-benzotrisulfides

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JP (1) JPS5265270A (en))
AR (1) AR221323A1 (en))
AU (1) AU503926B2 (en))
BE (1) BE846802A (en))
BR (1) BR7606511A (en))
CA (1) CA1071200A (en))
CH (1) CH620338A5 (en))
DE (1) DE2644036A1 (en))
FR (1) FR2326424A1 (en))
GB (2) GB1567482A (en))
MX (1) MX4134E (en))
NL (1) NL7610834A (en))
SE (1) SE7610167L (en))

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4139362A (en) * 1975-09-30 1979-02-13 The Ansul Company Biocidally-active 1,2,3-benzotrisulfides
US4240821A (en) * 1979-11-08 1980-12-23 Ciba-Geigy Corporation Biocidally-active 1,3-benzodithiole-2-thione compounds
US4287204A (en) * 1979-04-25 1981-09-01 Ciba-Geigy Corporation 1,3-Benzodithiol-2-ones
US20070129254A1 (en) * 2003-05-07 2007-06-07 Lindner Gregory J Homogeneous liquid saccharide and oil systems

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2399210A1 (fr) * 1977-08-04 1979-03-02 Ansul Co Produit antiparasitaire a base de 1,3-benzodithiole-2-thione
US5833944A (en) * 1994-11-07 1998-11-10 Hybridon, Inc. Procedure for the solid phase synthesis of 35 S-labeled oligonucleotides with 3H-1,2-benzodithiol-3-one-1,1-dioxide

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GB823251A (en) * 1955-07-02 1959-11-11 Thomae Gmbh Dr K Improvements in or relating to preparations containing benzoxathiol derivatives for the care of hair and skin
US3818041A (en) * 1969-09-10 1974-06-18 Standard Oil Co Process for preparing aromatic cyclic thiones

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US3491119A (en) * 1967-01-19 1970-01-20 Standard Oil Co Benzotrithiolanes and their preparation
US4084954A (en) * 1975-09-30 1978-04-18 The Ansul Company Biocidally-active 1,3-benzodithiole-2-one compounds

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GB823251A (en) * 1955-07-02 1959-11-11 Thomae Gmbh Dr K Improvements in or relating to preparations containing benzoxathiol derivatives for the care of hair and skin
US3818041A (en) * 1969-09-10 1974-06-18 Standard Oil Co Process for preparing aromatic cyclic thiones

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4139362A (en) * 1975-09-30 1979-02-13 The Ansul Company Biocidally-active 1,2,3-benzotrisulfides
US4287204A (en) * 1979-04-25 1981-09-01 Ciba-Geigy Corporation 1,3-Benzodithiol-2-ones
US4240821A (en) * 1979-11-08 1980-12-23 Ciba-Geigy Corporation Biocidally-active 1,3-benzodithiole-2-thione compounds
US20070129254A1 (en) * 2003-05-07 2007-06-07 Lindner Gregory J Homogeneous liquid saccharide and oil systems
US8470742B2 (en) 2003-05-07 2013-06-25 Croda Americas Llc Homogeneous liquid saccharide and oil systems

Also Published As

Publication number Publication date
CH620338A5 (en)) 1980-11-28
GB1567482A (en) 1980-05-14
FR2326424A1 (fr) 1977-04-29
US4139362A (en) 1979-02-13
AR221323A1 (es) 1981-01-30
GB1567481A (en) 1980-05-14
NL7610834A (nl) 1977-04-01
FR2326424B1 (en)) 1981-10-09
CA1071200A (en) 1980-02-05
SE7610167L (sv) 1977-03-31
AU503926B2 (en) 1979-09-27
BR7606511A (pt) 1977-07-05
AU1828776A (en) 1978-04-06
MX4134E (es) 1982-01-06
JPS5265270A (en) 1977-05-30
DE2644036A1 (de) 1977-04-14
BE846802A (fr) 1977-01-17

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